A study of the molecular and electronic structure of iron(II) and ruthenium(II) 1,3-di- and 1,2,4-tri-phospholyl sandwich compounds by photoelectron spectroscopy and density functional theory

Synthesis and Properties of [NiCp*(2,5‐tBu2PC4H2)], a 20‐Valence‐Electron Phosphanickelocene

“…1,1',2,2',4,4'-hexa(tert-butyl)nickelocene is unknown and the cocondensation of nickel atoms with 1,2,4-tri(tert-butyl)cyclopentadiene gives the h 3 -cyclopentenyl nickel complex 21 [54] so it is possible that the 18ve structure observed in 11 [13] may reflect steric issues. [55] However, the hindrance in complex 10 [12] is rotationally quite nicely equilibrated and in this case the multiple tBu substitution alone seems unlikely to impose a ring-slipped 18ve configuration. The difference in the electronic structure can be more reasonably attributed to the lowered HOMO-LUMO gap in the polyphospholyl ligand and the consequent increase in its ligand field strength.…”

Lithiation and alkylation reactions of the tri-phosphaferrocenes, [Fe(η5-P3C2tBu2)(η5-C5R5)], (R=H and Me): Crystal and molecular structures of the LiFe(η4-P2C2tBu2PnBu)(η5-C5Me5)2 dimer, [Fe(η4-P2C2tBu2PnBuMe)(η5-C5Me5)] and cis-[PtCl2(PMe3)Fe(η4-P2C2tBu2PnBuMe)(η5-C5H5)]

“…The nature of the bonding in phosphaferrocenes and related phosphametallocenes containing the g 5 -ligated 3,5-ditertiarybutyl-1,2,4-triphospholyl ring system, has been explored by electrochemical measurements in solution and gas-phase photoelectron spectroscopic techniques, coupled with supportive DFT calculations [12,21,22]. These studies have established that replacement of CR fragments by P in the corresponding parent metallocene reduces the overall electron density at the metal centre.…”

“…Replacement of one or more CR fragments in the cyclopentadienyl ring systems by phosphorus in [Fe(g 5 -C 5 R 5 ) 2 ], (R = H; R = Me) [5,6], gives a wide variety of poly-phosphaferrocene derivatives typified by [Fe(g 5 -PC 4 H 2 R 2 )(g 5 -C 5 H 5 )] (R = H; R = Me) [7,8], [Fe(g 5 -PC 4 H 2 Me 2 ) 2 ] [9], [Fe(g 5 -P 2 C 3 t Bu 3 )(g 5 -C 5 R 5 )] (R = H [10]; R = Me [11]), [Fe(g 5 -P 2 C 3 t Bu 3 ) 2 ] [12], [Fe(g 5 -P 3 C 2 t Bu 2 ) (g 5 -C 5 R 5 )] (R = H [10]; R = Me [13]), [Fe(g 5 -P 3 C 2 Ph 2 )(g 5 -C 5 H 2 t Bu 3 )] [14], [Fe(g 5 -P 5 )(g 5 -C 5 Me 5 )] [15], [Fe(g 5 -P 3 C 2 t Bu 2 )(g 5 -P 2 C 3 t Bu 3 )] and [Fe(g 5 -P 3 C 2 t Bu 2 ) 2 ] [16].…”

Synthesis and structural characterisation of lanthanide and actinide phosphaorganometallic complexes derived from the 3,5-di-tert-butyl-1,2,4-triphospholyl ring anion, P3C2But−2: Crystal and molecular structures of [M(η5-P3C2But2)2(η2-P3C2But2)] (M=Sc, Y, Tm, and U)

“…Sc [3], Ti [4,5], V [6], Cr [17], Mn [18], Fe [7][8][9][10][11][12][13], Co [19], Ni [21][22][23][24][25], Ru [13][14][15][16], and Rh [16,20]) and main group elements (e.g. Ga [26], In [27][28][29], Tl [26], Sr [30], and Pb [31]).…”